The combination of carbon and nitrogen-rich co-substrates results in a better balance and increases the stability of the anaerobic co-digestion (AcoD) process. In this work, the AcoD process of waste from the leather industry (shavings and sludge) with waste from agriculture (oat straw) was assessed with regard to the energy (biogas production) and waste treatment efficiency (reduction of organic matter). The results indicate that the addition of untreated oat straw improved the AcoD process, increasing biogas production (25.44 mL of cumulative biogas/g of VSS added) by almost 60% when compared to the AcoD of only leather waste (16.17 mL/gVSS). Also, the effect of acid, alkaline, thermal, and the combination of these pretreatment techniques was evaluated on the lignocellulosic composition of oat straw and on methane yields. Pretreatments improved the characteristics and bioavailability of oat straw, particularly in methodologies that use alkali, with a significant increase in cellulose content accompanied by a decrease in hemicellulose and lignin content. However, the possible formation of secondary products or sterilization of important microorganisms did not reflect in a greater production of biogas: 21.06 mL/gVSS for oat straw pretreated only with HCl and 21.91 mL/gVSS for oat straw pretreated with HCl in autoclave; 5.20 mL/gVSS for oat straw pretreated with NaOH; and 3.43 mL/gVSS for oat straw pretreated with NaOH in autoclave; thermal pretreatment probably has generated toxic compounds from hemicellulose and cellulose degradation, which inhibited the AcoD process and, as consequence, virtually no biogas was produced.